Hydroxy functional alkyl polyurea

ABSTRACT

A hydroxy functional alkyl polyurea is disclosed having the formula: 
     
       
         
         
             
             
         
       
     
     wherein R comprises the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; or R comprises the reaction product of isocyanate and alkanol amine, but the isocyanate is not HDI when the alkanol amine is diethanol amine or monomethanol amine and the isocyanate is not IPDI when the alkanol amine is monomethanol amine; wherein each R1 is independently a hydrogen, alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. 
     Further disclosed is a coating comprising:
         a. A film forming resin; and   b. A hydroxy functional alkyl polyurea crosslinker having the formula:       

     
       
         
         
             
             
         
       
         
         
           
             wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, the residue of an isocyanurate, biuret, allophanate, glycoluril, benzoguanamine and/or polyetheramine wherein each R1 is independently a hydrogen, and alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. 
           
         
       
    
     Substrates coated at least in part with such a coating are also disclosed.

FIELD OF THE INVENTION

The present invention is directed to hydroxy functional alkyl polyureas. Coatings comprising such polyureas are also within the scope of the present invention, as are substrates coated at least in part with such a coating.

BACKGROUND OF THE INVENTION

Coatings are applied to numerous substrates to provide protective and/or decorative qualities. These coatings are often thermoset coatings, which cure upon reaction of a functional resin with a crosslinking agent having functionality that reacts with the functionality of the resin. Crosslinkers are often formaldehyde based. Many industries are interested in reducing if not eliminating formaldehyde in coatings. Coatings that are substantially, essentially or completely free of formaldehyde are desired. It is also desired by many industries to lower the temperature at which coatings cure.

SUMMARY OF THE INVENTION

The present invention is directed to a hydroxy functional alkyl polyurea having the formula:

wherein R comprises the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; wherein each R1 is independently a hydrogen, alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.

The present invention is also directed to a composition comprising a film forming resin; and a hydroxy functional alkyl polyurea crosslinker having the formula:

wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, the residue of an isocyanurate, biuret, allophanate, glycoluril, benzoguanamine and/or polyetheramine; wherein each R1 is independently a hydrogen, an alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.

The present invention is also directed to a hydroxy functional alkyl polyurea having the formula

wherein R1 is as described above and R10 comprises the reaction product of isocyanate and an alkanol amine, but the isocyanate is not HDI when the alkanol amine is diethanol amine or monomethanol amine and the isocyanate is not IPDI when the alkanol amine is monomethanol amine.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to hydroxy functional alkyl polyurea compounds as described below. Such compounds can be used in various compositions including coatings, adhesives, and sealants, and can function, for example, as crosslinkers in such compositions. The compounds may have the general formula:

wherein R comprises the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; wherein each R1 is independently a hydrogen, an alkyl or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. The R1 group may exclude ether linkages.

Other hydroxy functional alkyl polyureas of the present invention can have the general formula

where R1 is as described above and R10 comprises the reaction product of isocyanate and an alkanol amine, but the isocyanate is not HDI when the alkanol amine is diethanol amine or monomethanol amine and the isocyanate is not IPDI when the alkanol amine is monomethanol amine. Suitable isocyanates can include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-methylenedicyclohexyl diisocyanate (Des-W), tetramethylxylylene diisocyanate (TMXDI) and trimethyl hexamethylene diisocyanate (TMDI). Suitable alkanol amines include diisopropanolamine (DIPA), diethanol amine (DEA), and monomethanol amine. Any combination of isocyanate and alkanol amine can be used other than those specifically excluded. Particularly suitable is the reaction product of HDI with DIPA, IPDI with DIPA and IPDI with DEA. The reaction between the isocyanate and alkanol amine can be done by any means known in the art, such as those reported in U.S. Pat. No. 3,420,787.

The present invention is further directed to a coating comprising:

a. a film forming resin; and b. a hydroxy functional alkyl polyurea crosslinker having the formula:

wherein R2 comprises a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, or the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; wherein each R1 is independently a hydrogen, an alkyl group having 1 or more carbons, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. The R1 group may exclude ether linkages.

R and R2 may comprise the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine and/or polyetheramine. An isocyanurate will be understood as referring to a compound having three isocyanate groups, typically in ring form, and is sometimes referred to as a trimer. This can include compounds having one or more isocyanurate moieties. Isocyanurates can be purchased from COVESTRO and VENCORE X Chemical. Suitable commercially available isocyanurates include DESMODUR N 3300A, DESMODUR N3800, DESMODUR N3400, DESMODUR N3600, DESMODUR N3900, DESMODUR RC, VESTANAT T1890/100, EASAQUA WT 2102, EASAQUA X D 401, EASAQUA M 501, EASAQUA X D 803, EASAQUA M 502, EASAQUA X L 600. A particularly suitable hydroxy functional alkyl polyurea formed from an isocyanurate is shown below:

wherein R1 is as described above and each R3 independently comprises an alkyl, aryl, alkylaryl, arylalkyl, alicyclic, and/or polyetheralkyl group.

A particularly suitable hydroxy functional alkyl polyurea formed from a bis-isocyanurate is shown below:

wherein R1 and R3 are as described above.

A biuret will be understood as referring to a compound that results upon the condensation of two molecules of urea, and is sometimes referred to as a carbamylurea. Biurets are commercial available from VENCORE X Chemical and COVESTRO as, for example, DESMODUR N-75, DESMODUR N-100, and DESMODUR N-3200, HDB 75B, HDB 75M, HDB 75MX, HDB-LV. A particularly suitable hydroxy functional alkyl polyurea formed from a biuret is shown below:

wherein R1 is as described above, each R5 independently comprises an alkyl, aryl, alkylaryl, arylalkyl, alicyclic, and/or polyetheralkyl group and R6 comprises H or an alkyl group.

Uretidione is a dimer of diisocyanate, examples of which include DESMODUR N-3400 polyisocyanate, a blend of the trimer and uretidione of HDI. An example is shown below where R₅ is as described above:

An allophonate will be understood as referring to a compound made from urethane and isocyanate. A method for making an allophonate is described at Surface Coating, Vol 1, Raw material and their usage, Landon New York, Chapman and Hall, Page 106. The reaction is generally depicted below where R₅ and R₆ are as described above and R₇ comprises the residue of a primary alcohol:

A glycoluril will be understood as referring to a compound composed of two cyclic urea groups joined across the same two-carbon chain, a suitable examples of which includes the below:

Glycoluril is widely commercially available, such as from Sigma-Aldrich.

Benzoguanamine is also known as 6-phenyl-1,3,5-triazine-2,4-diamine and is commercially available from The Chemical Company, Jamestown, R.I.

A polyether amine will be understood as referring to a compound having one or more amine groups attached to a polyether backbone such as one characterized by propylene oxide, ethylene oxide, or mixed propylene oxide and ethylene oxide repeating units in their respective structures, such as, for example, one of the Jeffamine series products. Examples of such polyetheramines include aminated propoxylated pentaerythritols, such as Jeffamine XTJ-616, and those represented by Formulas (IV) through (VI).

According to Formula (IV) the polyether amine may comprise:

wherein y=0-39, x+z=1-68.

Suitable amine-containing compounds represented by Formula (IV) include, but are not limited to, amine-terminated polyethylene glycol such as those commercially available from Huntsman Corporation in its JEFFAMINE ED series, such as JEFFAMINE HK-511, JEFFAMINE ED-600, JEFFAMINE ED-900 and JEFFAMINE ED-2003, and amine-terminated polypropylene glycol such as in its JEFFAMINE D series, such as JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000 and JEFFAMINE D-4000.

According to Formula (V) the polyetheramine may comprise:

wherein each p independently is 2 or 3.

Suitable amine-containing compounds represented by Formula (V) include, but are not limited to, amine-terminated polyethylene glycol based diamines, such as Huntsman Corporation's JEFFAMINE EDR series, such as JEFFAMINE EDR-148 and JEFFAMINE EDR-176.

According to Formula (VI) the polyetheramine may comprise:

wherein R₈ is H or C₂H₅, m=0 or 1, a+b+c=5-85.

Suitable amine-containing compounds represented by Formula (VI) include, but are not limited to, amine-terminated propoxylated trimethylolpropane or glycerol, such as Huntsman Corporation's JEFFAMINE T series, such as JEFFAMINE T-403, JEFFAMINE T-3000 and JEFFAMINE T-5000.

Particularly suitable are di- and tri-amines, such as 4,7,10-trioxa-1,13-tridecanediamine, JEFFAMINE D400, JEFFAMINE D4000, JEFFAMINE D2000 and JEFFAMINE T403.

In all cases, R, R2 and R10 may be substituted or unsubstituted. R2, as noted above, may also comprise a substituted or unsubstituted C1 to C36 alkyl group and/or an aromatic group. For example, the alkyl group may have two to ten carbon atoms such as six carbon atoms. The alkyl group may derive from an isocyanate, such as a diisocyanate. Suitable examples include isophorone diisocyanate and hexamethylene isocyanate. The aromatic group may derive from an aromatic ring containing isocyanate, suitable examples of which include methylene diphenyl diisocyanate, toluene diisocyanate and tetramethylxylylene diisocyanate.

Certain hydroxy functional alkyl polyureas of, and/or used according to, the invention may be made by reacting an isocyanate-containing compound with amino alcohol. Any isocyanate-containing compound having at least two isocyanate groups can be used, such as any of those described above. It will be appreciated that the “R” “R2” or “R10” group will reflect the isocyanate-containing compound selected.

Similarly, any amino alcohol having two or more carbon atoms can be used, and the “R1” group will reflect the amino alcohol selected. The amino alcohol can have one, two or more hydroxyl functional groups. One or more amino alcohols can be used, which will result in different R1 groups being present on the polyurea. R1 can also be hydrogen or an alkyl group. Suitable amino alcohols include monoethanol amine, diethanol amine and diispropyl amine.

Generally, the hydroxyl functional alkyl polyureas can be made by reacting amino alcohol with an isocyanate-containing compound in an organic polar solvent, such as alcohol or water. The reaction temperate can be kept below 35° C. The equivalent ratio of amine to isocyanate can be 2-1:1-2, such as 1:1.

The hydroxy functional alkyl polyureas of, and/or used according to, the invention may be made by alternative methods as well. For example, amino alcohols can react with carbonate to form hydroxylalkyl carbamate, and hydroxylalkyl carbamate can further react with amines to form hydroxy functional alkyl polyureas.

The number average molecular weight (“Mn”) of the hydroxy functional alkyl polyurea can be 100 or greater, such as 350 or greater or 1000 or greater, and/or can be 6000 or lower, such as 3000 or lower, or 2000 or lower. Mn means the theoretical value as determined by Gel Permeation Chromatography using Waters 2695 separation module with a Waters 410 differential refractometer (RI detector)) and polystyrene standards. The range of molecular weights of the polystyrene standards for this method is from approximately 800 to 900,000 g/mol. In determining Mn according to the invention, the above method was used. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 ml min-1, and two PL Gel Mixed C columns were used for separation.

The present invention is further directed to a composition comprising a film forming resin and any of the hydroxy functional alkyl polyureas as described above. The composition can be, for example, a coating, an adhesive or a sealant. It will be appreciated that coatings, sealants and adhesives often comprise similar components but are formulated differently depending on the needs of the user. The hydroxy functional alkyl polyurea will typically react with the film forming resin to form the cured composition. For example, in a coating the polyurea will act as a crosslinking agent and react with the film forming resin to form a cured coating. Accordingly, the compositions of the present invention can achieve cure without formaldehyde-based crosslinking agents. “Formaldehyde-based crosslinking agents” will be understood as those made by reacting amino compounds with formaldehyde followed by esterification with alkanols. Examples include, melamine formaldehyde crosslinkers like hexamethylol melamine and trimethylol melamine and aminoplast crosslinkers. When used as a crosslinker, the hydroxy functional alkyl polyurea may be used alone or in combination with one or more additional crosslinkers known in the art to crosslink, for example, with functionality on the film-forming resin. One skilled in the art can select an appropriate crosslinker based on this functionality from known crosslinkers such as melamine, phenolic, carbodiimide, hydroxyalkylamide, isocyanate, blocked isocyanate, benzaguanamine, TGIC, epoxies, oxazolines, and the like.

Any film forming resin that will react with the hydroxy functional alkyl polyurea can be used according to the present invention. The film-forming resin can be selected from, for example, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, polysiloxane polymers, copolymers thereof, and mixtures thereof. Generally, these polymers can be any polymers of these types made by any method known to those skilled in the art. Such polymers may be solvent-borne or water-dispersible, emulsifiable, or of limited water solubility. The functional groups on the film-forming resin may be selected from any of a variety of reactive functional groups including, for example, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups) mercaptan groups, and combinations thereof. Appropriate mixtures of film-forming resins may also be used in the preparation of the present compositions, as can additional crosslinkers as noted above.

The composition can comprise, for example, 10 weight percent or greater of film forming resin, such as 50 weight percent or greater or 75 weight percent or greater and/or can comprise 99 weight percent or lower of film forming resin, such as 80 weight percent or lower or 70 weight percent or lower, with weight percent based on total solid weight of the coating. The composition can comprise, for example, 0.5 weight percent or greater of hydroxy functional alkyl polyurea, such as 2 weight percent or greater or 7 weight percent or greater, and/or can comprise 30 weight percent or lower hydroxy functional alkyl polyurea, such as 20 weight percent or lower or 15 weight percent or lower, with weight percent based on total solid weight of the coating.

The composition may comprise one or more solvents including water or organic solvents. Suitable organic solvents include glycols, glycol ether alcohols, alcohols, ketones, and aromatics, such as xylene and toluene, acetates, mineral spirits, naphthas and/or mixtures thereof. “Acetates” include the glycol ether acetates. The solvent can be a non-aqueous solvent. “Non-aqueous solvent” and like terms means that less than 50% of the solvent is water. For example, less than 10%, or even less than 5% or 2%, of the solvent can be water. It will be understood that mixtures of solvents, including or excluding water in an amount of less than 50%, can constitute a “non-aqueous solvent”. The composition may be aqueous or water-based. This means that 50% or more of the solvent is water. These embodiments have less than 50%, such as less than 20%, less than 10%, less than 5% or less than 2% solvent.

The composition may be in solid particulate form, i.e. a powder coating. Such coatings will be appreciated as being environmentally friendly, as only water is released on cure.

The compositions of the present invention may further comprise a catalyst. Any catalyst typically used to catalyze crosslinking between a hydroxyl group and an acid may be used. Examples of such a catalyst include those having metal complexes with metals such as zinc, zirconium, titanium and tin and other Lewis acids. Amines, including guanamines, may also be used. The use of a catalyst, it will be appreciated, causes the cure of the coating to occur faster. Notably, catalysts are not effective at speeding the cure of beta-hydroxyl alkyl amides with the film forming resins listed above. Accordingly, it was a surprising result that catalysts promoted cure in the present coatings.

If desired, the compositions can comprise other optional materials well known in the art of formulating, such as colorants, plasticizers, abrasion resistant particles, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic cosolvents, reactive diluents, catalysts, grind vehicles, slip agents, moisture scavenger and other customary auxiliaries.

As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect, e.g. gloss, to the composition. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings of the present invention.

Example colorants include matting pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by grinding or simple mixing. Colorants can be incorporated by grinding into the coating by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.

Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black, carbon fiber, graphite, other conductive pigments and/or fillers and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably.

Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as acid dyes, azoic dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, perylene aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenyl methane.

Example tints include, but are not limited to, pigments dispersed in water-based or water-miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemicals, Inc.

As noted above, the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Pat. No. 6,875,800 B2, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution). In order to minimize re-agglomeration of nanoparticles within the coating, a dispersion of resin-coated nanoparticles can be used. As used herein, a “dispersion of resin-coated nanoparticles” refers to a continuous phase in which is dispersed discreet “composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle. Example dispersions of resin-coated nanoparticles and methods for making them are described, for example, in U.S. Pat. No. 7,605,194 at column 3, line 56 to column 16, line 25, the cited portion of which being incorporated herein by reference.

Example special effect compositions that may be used include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color-change. Additional special effect compositions can provide other perceptible properties, such as opacity or texture. For example, special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles. Example color effect compositions are identified in U.S. Pat. No. 6,894,086, incorporated herein by reference. Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air.

A photosensitive composition and/or photochromic composition, which reversibly alters its color when exposed to one or more light sources, can be used in the coating of the present invention. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns. For example, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds. Example photochromic and/or photosensitive compositions include photochromic dyes.

The photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component. In contrast to some coatings in which the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with the present invention, have minimal migration out of the coating. Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in U.S. Pat. No. 8,153,344, and incorporated herein by reference.

In general, the colorant can be present in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise from 1 to 65 weight percent of the present compositions, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the compositions.

An “abrasion resistant particle” is one that, when used in a coating, will impart some level of abrasion resistance to the coating as compared with the same coating lacking the particles. Suitable abrasion resistant particles include organic and/or inorganic particles. Examples of suitable organic particles include but are not limited to diamond particles, such as diamond dust particles, and particles formed from carbide materials; examples of carbide particles include but are not limited to titanium carbide, silicon carbide and boron carbide. Examples of suitable inorganic particles, include but are not limited to silica; alumina; alumina silicate; silica alumina; alkali aluminosilicate; borosilicate glass; nitrides including boron nitride and silicon nitride; oxides including titanium dioxide and zinc oxide; quartz; nepheline syenite; zircon such as in the form of zirconium oxide; buddeluyite; and eudialyte. Particles of any size can be used, as can mixtures of different particles and/or different sized particles. For example, the particles can be microparticles, having an average particle size of 0.1 to 50, 0.1 to 20, 1 to 12, 1 to 10, or 3 to 6 microns, or any combination within any of these ranges. The particles can be nanoparticles, having an average particle size of less than 0.1 micron, such as 0.8 to 500, 10 to 100, or 100 to 500 nanometers, or any combination within these ranges.

Any slip agent can be used according to the present invention such as those commercial available from BYK Chemie or Dow Corning. A wax can also be used such as polyolefin wax, silicone or paraffin.

The hydroxy functional alkyl polyureas, and/or the compositions of the present invention, may be substantially free, may be essentially free and/or may be completely free of bisphenol A and epoxy compounds derived from bisphenol A (“BPA”), such as bisphenol A diglycidyl ether (“BADGE”). Such compounds are sometimes referred to as “BPA non intent” because BPA, including derivatives or residues thereof, are not intentionally added but may be present in trace amounts because of impurities or unavoidable contamination from the environment. The hydroxy functional alkyl polyureas and/or coatings can also be substantially free and may be essentially free and/or may be completely free of bisphenol F and epoxy compounds derivatived from bisphenol F, such as bisphenol F diglycidyl ether (“BFDGE”). The term “substantially free” as used in this context means the and/or coatings contain less than 1000 parts per million (ppm), “essentially free” means less than 100 ppm and “completely free” means less than 20 parts per billion (ppb) of any of the above mentioned compounds, derivatives or residues thereof.

In addition, the hydroxy functional alkyl polyureas and/or the composition of the present invention may be substantially free, may be essentially free and/or may be completely free of formaldehyde. The term “substantially free” as used in this context means the and/or coatings contain less than 1000 parts per million (ppm), “essentially free” means less than 100 ppm and “completely free” means less than 100 parts per billion (ppb) of formaldehyde compounds, derivatives or residues thereof.

The present compositions can be applied to any substrates known in the art, for example, automotive substrates, marine substrates, industrial substrates, packaging substrates, wood flooring and furniture, apparel, electronics including housings and circuit boards and including consumer electronics such as housings for computers, notebooks, smartphones, tablets, televisions, gaming equipment, computer equipment, computer accessories, MP3 players, and the like, glass and transparencies, sports equipment including golf balls, and the like. These substrates can be, for example, metallic or non-metallic. Metallic substrates include tin, steel, tin-plated steel, chromium passivated steel, galvanized steel, aluminum, aluminum foil. Metal sheet as used herein refers to flat metal sheet and coiled metal sheet, which is coiled, uncoiled for coating and then re-coiled for shipment to a manufacturer. Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (“PET”), polycarbonate, polycarbonate acrylobutadiene styrene (“PC/ABS”), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, and the like. The substrate can be one that has been already treated in some manner, such as to impart visual and/or color effect. Suitable substrates can include those in which powder coatings are typically applied.

The compositions of the present invention can be applied by any means standard in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, and the like.

The compositions can be applied to a dry film thickness of 0.04 mils to 4 mils, such as 0.3 to 2 or 0.7 to 1.3 mils. The compositions can also be applied to a dry film thickness of 0.1 mils or greater, 0.5 mils or greater 1.0 mils or greater, 2.0 mils or greater, 5.0 mils or greater, or even thicker. In some applications, a dry film thickness of 1-20 microns, such as 2-6 microns, is desired.

The compositions of the present invention can be used alone, or in combination with one or more other compositions, such as a coating system having two or more layers. For example, the compositions of the present invention can comprise a colorant or not and can be used as a primer, basecoat, and/or top coat. For substrates coated with multiple coatings, one or more of those coatings can be coatings as described herein. The present coatings can also be used as a packaging “size” coating, wash coat, spray coat, end coat, and the like.

It will be appreciated that the compositions described herein can be either one component (“1K”), or multi-component compositions such as two component (“2K”) or more. A 1K composition will be understood as referring to a composition wherein all the coating components are maintained in the same container after manufacture, during storage, etc. A 1K composition can be applied to a substrate and cured by any conventional means, such as by heating, forced air, and the like. The present compositions can also be multi-component, which will be understood as compositions in which various components are maintained separately until just prior to application. As noted above, the present compositions can be thermoplastic or thermosetting.

The composition can be a clearcoat. A clearcoat will be understood as a coating that is substantially transparent or translucent. A clearcoat can therefore have some degree of color, provided it does not make the clearcoat opaque or otherwise affect, to any significant degree, the ability to see the underlying substrate. The clearcoats of the present invention can be used, for example, in conjunction with a pigmented basecoat. The clearcoat can be formulated as is known in the coatings art.

The composition may also comprise a colorant, such as a pigmented basecoat used in conjunction with a clearcoat, or as a pigmented monocoat. Such coating layers are used in various industries to impart a decorative and/or protective finish. For example, such a coating or coating system may be applied to a vehicle. “Vehicle” is used herein in its broadest sense and includes all types of vehicles, such as but not limited to cars, trucks, buses, vans, golf carts, motorcycles, bicycles, railroad cars, airplanes, helicopters and the like. It will be appreciated that the portion of the vehicle that is coated according to the present invention may vary depending on why the coating is being used. For example, anti-chip primers may be applied to some of the portions of the vehicle as described above. When used as a colored basecoat or monocoat, the present coatings will typically be applied to those portions of the vehicle that are visible such as the roof, hood, doors trunk lid and the like, but may also be applied to other areas such as inside the trunk, inside the door and the like especially when the compositions are formulated as sealants or adhesives; they can also be applied to those portions of the car that are in contact with the driver and/or passengers, such as the steering wheel, dashboard, gear shift, controls, door handle and the like. Clearcoats will typically be applied to the exterior of a vehicle.

The compositions of the present invention are also suitable for use as packaging coatings. The application of various pretreatments and coatings to packaging is well established. Such treatments and/or coatings, for example, can be used in the case of metal cans, wherein the treatment and/or coating is used to retard or inhibit corrosion, provide a decorative coating, provide ease of handling during the manufacturing process, and the like. Coatings can be applied to the interior of such cans to prevent the contents from contacting the metal of the container. Contact between the metal and a food or beverage, for example, can lead to corrosion of a metal container, which can then contaminate the food or beverage. This is particularly true when the contents of the can are acidic in nature. The coatings applied to the interior of metal cans also help prevent corrosion in the headspace of the cans, which is the area between the fill line of the product and the can lid; corrosion in the headspace is particularly problematic with food products having a high salt content. Coatings can also be applied to the exterior of metal cans. Certain coatings of the present invention are particularly applicable for use with coiled metal stock, such as the coiled metal stock from which the ends of cans are made (“can end stock”), and end caps and closures are made (“cap/closure stock”). Since coatings designed for use on can end stock and cap/closure stock are typically applied prior to the piece being cut and stamped out of the coiled metal stock, they are typically flexible and extensible. For example, such stock is typically coated on both sides. Thereafter, the coated metal stock is punched. For can ends, the metal is then scored for the “pop-top” opening and the pop-top ring is then attached with a pin that is separately fabricated. The end is then attached to the can body by an edge rolling process. A similar procedure is done for “easy open” can ends. For easy open can ends, a score substantially around the perimeter of the lid allows for easy opening or removing of the lid from the can, typically by means of a pull tab. For caps and closures, the cap/closure stock is typically coated, such as by roll coating, and the cap or closure stamped out of the stock; it is possible, however, to coat the cap/closure after formation. Coatings for cans subjected to relatively stringent temperature and/or pressure requirements should also be resistant to popping, corrosion, blushing and/or blistering.

Accordingly, the present invention is further directed to a package coated at least in part with any of the coating compositions described above. A “package” is anything used to contain another item, particularly for shipping from a point of manufacture to a consumer, and for subsequent storage by a consumer. A package will be therefore understood as something that is sealed so as to keep its contents free from deterioration until opened by a consumer. The manufacturer will often identify the length of time during which the food or beverage will be free from spoilage, which typically ranges from several months to years. Thus, the present “package” is distinguished from a storage container or bakeware in which a consumer might make and/or store food; such a container would only maintain the freshness or integrity of the food item for a relatively short period. A package according to the present invention can be made of metal or non-metal, for example, plastic or laminate, and be in any form. An example of a suitable package is a laminate tube. Another example of a suitable package is metal can. The term “metal can” includes any type of metal can, container or any type of receptacle or portion thereof that is sealed by the food/beverage manufacturer to minimize or eliminate spoilage of the contents until such package is opened by the consumer. One example of a metal can is a food can; the term “food can(s)” is used herein to refer to cans, containers or any type of receptacle or portion thereof used to hold any type of food and/or beverage. The term “metal can(s)” specifically includes food cans and also specifically includes “can ends” including “E-Z open ends”, which are typically stamped from can end stock and used in conjunction with the packaging of food and beverages. The term “metal cans” also specifically includes metal caps and/or closures such as bottle caps, screw top caps and lids of any size, lug caps, and the like. The metal cans can be used to hold other items as well, including, but not limited to, personal care products, bug spray, spray paint, and any other compound suitable for packaging in an aerosol can. The cans can include “two piece cans” and “three-piece cans” as well as drawn and ironed one-piece cans; such one piece cans often find application with aerosol products. Packages coated according to the present invention can also include plastic bottles, plastic tubes, laminates and flexible packaging, such as those made from PE, PP, PET and the like. Such packaging could hold, for example, food, toothpaste, personal care products and the like.

The coating can be applied to the interior and/or the exterior of the package. For example, the coating can be rollcoated onto metal used to make a two-piece food can, a three-piece food can, can end stock and/or cap/closure stock. The coating is applied to a coil or sheet by roll coating; the coating is then cured by radiation and can ends are stamped out and fabricated into the finished product, i.e. can ends. The coating could also be applied as a rim coat to the bottom of the can; such application can be by roll coating. The rim coat functions to reduce friction for improved handling during the continued fabrication and/or processing of the can. The coating can also be applied to caps and/or closures; such application can include, for example, a protective varnish that is applied before and/or after formation of the cap/closure and/or a pigmented enamel post applied to the cap, particularly those having a scored seam at the bottom of the cap. Decorated can stock can also be partially coated externally with the coating described herein, and the decorated, coated can stock used to form various metal cans.

Metal coils, having wide application in many industries, are also substrates that can be coated according to the present invention. Coil coatings also typically comprise a colorant.

After application to the substrate, the coating composition may be cured by any appropriate means. In some applications a cure of 140° C. or lower, such as 130° C. or lower or 125° C. or lower for 30 minutes or less, such as y minutes or less may be desired and can be achieved according to the present invention. In other applications a cure of 250° C. or lower, such as 235° C. or lower or 200° C. or lower but for a time of three minutes or less, such as two minutes or less, or one minute or less, or 30 seconds or less or 15 seconds or less, may be desired and can be achieved according to the present invention. Accordingly, the present coatings can be used across a broad range of industries and cure conditions.

In addition to their use in compositions as described above, HAU compounds as described herein can be used in thermoplastic acid functional polymers such polyesters, ethylene acrylic acid copolymers and terpolmers, and ionomers. In melt blends with thermoplastic polymers, HAU compounds can serve as cross-linkers, chain extenders, to increase the hydrolysis resistance of polyesters, and modify viscosity for applications such as extruded fibers, films, injection molded articles, extrusion coating, blow molding, extrusion blowmolding, and extrusion. HAU can also be used in applications currently employing carbodiimide additives.

As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to “a” hydroxy functional alkyl polyurea, “a” film forming resin, “an” isocyanate, “an” alkanol amine, “the” residue of “an”, and the like, one or more of each of these and any other components can be used. As used herein, the term “polymer” refers to oligomers and both homopolymers and copolymers, and the prefix “poly” refers to two or more. Including, for example and like terms means including for example but not limited to. When ranges are given, any endpoints of those ranges and/or numbers within those ranges can be combined within the scope of the present invention.

Non-limiting aspects of the invention include:

1. A hydroxy functional alkyl polyurea having the formula:

wherein R comprises the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; or R comprises the reaction product of an isocyanate and an alkanol amine but the isocyanate is not HDI when the alkanol amine is diethanol amine or monomethanol amine and the isocyanate is not IPDI when the alkanol amine is monomethanol amine; wherein each R1 is independently a hydrogen, alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. 2. The polyurea of aspect 1, wherein R comprises the residue of an isocyanurate. 3. The polyurea of any preceeding aspect, wherein at least one R1 comprises an ethanol or isopropanol group. 4. A composition comprising:

-   -   a. A film forming resin; and     -   b. A hydroxy functional alkyl polyurea crosslinker having the         formula:

-   -   -   wherein R2 is a substituted or unsubstituted C1 to C36 alkyl             group, an aromatic group, the residue of an isocyanurate,             biuret, allophanate, glycoluril, benzoguanamine and/or             polyetheramine; wherein each R1 is independently a hydrogen,             an alkyl having at least 1 carbon, or a hydroxy functional             alkyl having 2 or more carbons; and n is 2-6.             5. The composition of any preceding aspect, wherein R             comprises a substituted or unsubstituted C2-C12.             6. The composition of any preceding aspect, wherein R             comprises a substituted or unsubstituted C6             7. The composition of any preceding aspect, wherein R1             comprises ethanol or isopropanol.             8. The composition of any preceding aspect, wherein the             coating is substantially formaldehyde free.             9. The composition of any preceding aspect, wherein the             coating is a powder coating.             10. The composition of any preceding aspect, further             comprising a catalyst.             11. The composition of any preceding aspect, wherein the             catalyst comprises tin and/or titanium.             12. The composition of any preceding aspect, wherein the             composition is a coating.             13. The coating of any preceding aspect, wherein the coating             cures at a temperature of 130° C. or lower in less than 30             minutes, or wherein the coating cures at a temperature of             250° C. or lower for fifteen seconds or less.             14. The composition of any preceding aspect, wherein the R1             groups do not contain an ether linkage.             15. A substrate coated at least in part with the composition             of any preceding aspect.             16. The substrate of any preceding aspect wherein the             substrate comprises a package.             17. The substrate of any preceding aspect wherein the             substrate comprises a metal can.             18. The substrate of any preceding aspect wherein the             substrate comprises a vehicle.             19. The substrate of any preceding aspect, wherein the             substrate is rubber or plastic.             20. The coating of any preceding aspect, wherein the film             forming resin comprises polyurethane.             21. The coating of any preceding aspect, wherein the film             forming resin comprises acrylic latex, such as one having an             acid value of 10 to 15 mg KOH/g such as 10 mg KOH/g or             greater.             22. The coating of any preceding aspect, wherein the film             forming resin comprises a polyurethane acrylic latex.             23. The coating of any preceding aspect, wherein the film             forming resin comprises an acrylic resin.             24. The coating of any preceding aspect, wherein R2             comprises a dialkylamine.             25. The coating of any preceding aspect, wherein R₂             comprises diethylene triamine.             26. The coating of any preceding aspect, wherein R₂             comprises amine functional amide.

EXAMPLES

The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.

Example 1 Synthesis of 1,1,6,6-hexamethylene-3,3,3′,3′-tetrakis(2-hydroxyethyl)-bis-urea

315.4 g diethanolamine and 473.13 g DI water were charged into a 2 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 252.1 g 1,6-hexamethylenediisocyanate (HDI) was added into reaction mixture to maintain temperate below 30° C. by using cooling bath. After finishing addition of HDI, the reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm-1). A clear solution was obtained and used as crosslinker.

Example 2 Synthesis of 1,1,6,6-hexamethylene-3,3,3′,3′-tetrakis(2-hydroxypropyl)-bis-urea

199.8 g diisopropanolamine and 299.7 g DI water were charged into a 2 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 126.1 g 1,6-hexamethylenediisocyanate (HDI) was added into reaction mixture to maintain temperate below 30° C. by using cooling bath. After finishing addition of HDI, the reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm-1). A clear solution was obtained and used as crosslinker.

Example 3 Synthesis of Tetrakis(2-hydroxyethyl)-bis-urea from IPDI

315.4 g diethanolamine and 552 g DI water were charged into a 2 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 333.4 g isophorone diisocyanate (IPDI) was added into reaction mixture to maintain temperate below 30° C. by using cooling bath. After finishing addition of IPDI, the reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 4 Synthesis of Tetrakis(2-hydroxypropyl)-bis-urea from IPDI

199.8 g diisopropanolamine and 299.7 g DI water were charged into a 2 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 166.7 g isophorone diisocyanate (IPDI) was added into reaction mixture to maintain temperate below 30° C. by using cooling bath. After finishing addition of IPDI, the reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 5 Synthesis of Polymeric HAU from HDI Trimer

105.1 g diethanolamine and 315.4 grams of DI water were charged into a 1 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 193.4 g DESMODUR N3300A (HDI trimer) was added into reaction mixture to maintain temperate below 30° C. by using cooling bath. After finishing addition of HDI trimer, 105.1 g DOWANOL PM was used to rinse the addition funnel. The reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 6 Synthesis of HAU from HDI Trimer

166.5 g diisopropanolamine and 333 grams of DI water charged into a 1 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 214.25 grams of DESMODUR N3300A (HDI trimer) was added into reaction mixture to maintain temperature below 30° C. by using a cooling bath. After finishing addition of HDI trimer, 300 grams of Dowanol PM was used to rinse the addition funnel. The reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 7 Synthesis of Polymeric HAU from IPDI Trimer

105.1 g diethanolamine, 262.9 grams of DI water, and 157.7.6 g DOWANOL PM were charged into a 1 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. A solution of 242.8 g IPDI trimer in 242.8 g MIBK was added into reaction mixture to maintain temperate below 20° C. by using cooling bath. After finishing addition of IPDI trimer, 10 g Dowanol PM was used to rinse the addition funnel. The reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 8 Synthesis of Polymeric HAU from IPDI Trimer

133.2 g diisopropanolamine, 199.7 grams of DI water, and 236.6 g DOWANOL PM were charged into a 1 L flask equipped with a stirrer, a condenser, and a thermocouple in a cooling bath. 360 g DESMODUR Z 4470 BA (IPDI trimer in butyl acetate) was added into reaction mixture to maintain temperature below 30° C. by using cooling bath. After finishing addition of IPDI trimer, 100 g DOWANOL PM was used to rinse the addition funnel. The reaction mixture was allowed to stand at room temperature until the NCO peak was gone as evidenced by IR (2260 cm⁻¹). A clear solution was obtained and used as crosslinker.

Example 9 Coating Compositions

Example 9A—A OH terminated polyurethane was prepared by the following procedure. 100 g of 2-ethylhexyl acrylate (EHA), 79.2 g of hydroxyethyl methacrylate (HEMA), 1.5 g of 2,6-di-tert-butyl 4-methyl phenol, 0.78 g of triphenyl phosphite, 0.78 g of dibutyl tin dilaurate, 405 g of polytetrahydrofuran with number average molecular weight 1000, 81.6 g of dimethyol propionic acid, and 4 g of triethyl amine were charged in order into a four necked round bottom flask fitted with a thermocouple, mechanical stirrer, and condenser. The mixture was heated to 90° C. and held for 15 minutes. After that, 405.5 g of isophorone diisocyanate was charged into the flask over 90 minutes. After that, the isocyanate adding funnel was rinsed with 20 g of 2-ethylhexyl acrylate. The mixture was held at 90° C. until all of the isocyanate IR peak was gone. After that, 454 g of 2-ethylhexyl acrylate and 72.5 DOWANOL PM were charged into flask, and cooled to ambient temperature. The acid value of the polyurethane was measure to be 23.5 mgKOH/g, and weight average molecular weight by GPC was 7269.

Example 9B—A carboxyl functionalized polyurethane/acrylic latex was prepared as follows. 545 g of deionized water, 15.6 g of AEROSOL OT-75 from Cytec, 10.7 g of dimethyl ethanolamine, 298 g of the OH terminated polyurethane prepared according to Example 9A, 74.4 g of methyl methacrylate, and 11.1 g of hexanediol diacrylate was charged in order to a four necked round bottom flask fitted with a thermocouple, mechanical stirrer, and condenser. The mixture was heated to 33° C. and held for 30 minutes with a N₂ blanket. After that, a mixture of 0.38 g of t-butylhydroperoxide and 15 g of deionized water was charged into the flask, and mixed for 15 minutes. A mixture of 0.008 g ferrous ammonium, sulfate, 0.38 g sodium metabisulfite and 15 g of deionized water was charged into the flask over 30 minutes. During this charge, exotherm was expected. After peak exotherm, the system was held at 65° C. for 1 hour. After it was cooled to 45° C., 3.5 g of aciticide MBS from Thor GmbH, 0.18 g of FOAMKILL 649 from Crucible Chemical, and 1.5 g of deionized water were charged into flask and mixed for 15 minutes.

The resulting latex had a solid content of 38.5%, and the volume average particle size measured by Zetasizer was 104 nm.

Example 10

Different hydroxyl functional alkyl polyureas of the present invention were mixed with the acid functional polymer of Example 9B at a COOH/OH ratio of 1/1. The mixture was drawn down to panel with a wet thickness of 100 micrometer. The film was dried at room temperature for 15 minutes, and followed by baking at different temperatures for 30 minutes. After cooling at room temperature for 30 minutes, panels were tested for MEK double rubs. Into separate samples of solution containing the polymer of 9B and the hydroxyl functional alkyl polyureas was added 1% TYZOR LA (catalyst, available from Dorf Ketal Chemical, LLC). This solution was drawn down on a panel, followed by a 30 minutes bake at different temperature and tested for MEK double rubs.

As shown in the following Table 1, when TYZOR LA was used, MEK double rubs were significantly higher than samples without the catalyst particularly at 130° C.

TABLE 1 TYZOR Cure temperature (° C.) Hydroxyl functional alkyl polyurea LA 130 140 Example 1 0 35 90 Example 1 1% 130 150 Example 2 0 30 80 Example 2 1% 110 150 Example 3 0 40 80 Example 3 1% 110 150 Example 4 0 40 70 Example 4 1% 70 150 Example 5 0% 35 70 DEA/HDI trimer Example 5 DEA/HDI trimer 1% 110 150 Example 6 0% 30 80 DIPA/HDI trimer Example 6 DIPA/HDI trimer 1% 90 150 Example 7 DEA/IPDI trimer 0% 30 70 Example 7DEA/IPDI trimer 1% 35 110 Example 8 DIPA/IPDI trimer 0% 20 60 Example 8 DIPA/IPDI trimer 1% 60 110

Example 11

Polyurea Example 1 and acid functionalized PU/acrylate (example 9B) were mixed at a COOH/OH ratio of 1/1 and different catalyst as shown below (1% based on mixture) were mixed in. The mixtures were then drawn down to panel with a wet thickness of 100 micrometer. The film was dried at room temperature for 15 minutes, and followed by baking at different temperature for 30 minutes. After cooling at room temperature for 30 minutes, panels were tested for MEK double rubs.

As shown in the following Table 2, TYZOR LA, TYZOR 131 (catalyst, available from Dorf Ketal Chemical, LLC), and DBTDL performed better than control without catalyst.

TABLE 2 Catalyst catalyst level MEK duble rubs none 0 35 TYZOR LA 1% 130 TYZOR 131 1% 70 DBTDL 1% 100

Example 12

Polyurea Example 1 and TYZOR LA (1% based on mixture) were mixed with acid functionalized PU/acrylate (example 9B) at a COOH/OH ratio of 1/1. The mixture was then drawn down to panel with a wet thickness of 100 micrometer. The film was dried at room temperature for 15 minutes, and followed by baking at different temperature for 30 minutes. After cooling at room temperature for 30 minutes, panels were tested with different solvent for double rubs.

As shown in the following Table 3, with 1% TYZOR as catalyst, film resistance to solvents are significantly better than film without catalyst.

TABLE 3 TYZOR LA 0 1.00% Cure T (° C.) 130 140 130 140 acetone 20 70 70 150 DOWANOL PM 20 80 60 150 MEK 40 110 130 150 butyl acetate 150 130 150 150 A100 120 150 150 150 hexane 150 150 150 150 water 150 150 150 150

Example 13 Beverage can Overvarnish Cured with HAU

The coating of Example 13 was prepared by combining all of the materials shown in Table Y and mixing for 10 minutes with a mixing blade.

TABLE Y Material Description Amount Water reducible acrylic (255 Internally produced by PPG* 190.43 acid value on 100% solids) DI Water De-ionized water 18.0 DIPA/HDI trimer (Example 6) HAU crosslinker 107.94 Tyzor LA Organic titanate from Dorf Ketal 1.99 BYK-333 Slip agent from BYK 0.3 Total 318.66 *A suitable acrylic resin can be prepared, for example, according to the procedures outlined by Hellring in Example 1 of US patent application 2015/0280239 Al.

Coated panels were obtained by drawing the coating over chrome treated 5182-H48 aluminum panels using a wire wound rod to obtain dry coating weights of 2.0-2.5 mg/square inch (msi). The coated panels were immediately placed into a one-zone, gas-fired, conveyor oven for 15 seconds and baked to a peak metal temperature of 400° F. (204° C.) or 320° F. (160° C.). The baked panels were immediately tested for hot tack cure test.

In the hot tack cure test, the minimum cure temperature was determined for a film to achieve resistance to damage when rubbed at an elevated temperature and compared to a control.

Once the panel exited the oven, the panel was immediately placed on a 60° C. hot plate. Typically the hot plate temperature is controlled to mimic the can temperature as measured at the “deco oven” exit on a commercial can line. Using a gauze (4″×4″-12 ply gauze pad) covered 2 lb. hammer, the panel was held against the hot plate for at least 5 seconds. Resting the gauze covered hammer head on the panel, the coated surface was double rubbed 5 times. The tack resistance was rated for mar resistance.

TABLE 5 PPG3805803 Waterborne Example 1 Overvarnish from PPG 1^(st) Bake (PMT) 204° C. 160° C. 204° C. 160° C. 60° C. Hot Tack Test None None Very Slight Severe Mar Rating (Pass) (Pass) (Pass) (Fail)

A second bake was subsequently applied to the panel to simulate an inside spray bake and to obtain the final properties of the overvarnish. The baked panel from the gas conveyor oven was placed in a 204C box oven for 3 minutes. The panels were cooled down and evaluated for MEK double rubs and Joy Detergent tests.

The MEK double rub test rub used a gauze covered hammer that was saturated with methyl ethyl ketone. The coatings were evaluated for the number of double rubs it took to soften and break through the coating or until 50 double rubs were performed. The coatings were also evaluated for their ability to adhere to the aluminum panels and to resist blushing in the Joy detergent test. The results of the test are reported in Table 2.

Blush Resistance: Blush resistance measured the ability of a coating to resist attack by various testing solutions. When the coated film absorbs test solution, it generally becomes cloudy or looks white. Blush was measured visually using a scale of 1-10 where a rating of “10” indicates no blush and a rating of “0” indicates complete whitening of the film. Blush ratings of at least 6 are typically desired for commercially viable coatings. The coated panel tested was 2×4 inches (5×10 cm) and the testing solution covered half of the panel being tested so you can compare blush of the exposed panel to the unexposed portion.

Adhesion: Adhesion testing was performed to assess whether the coating adheres to the substrate. The adhesion test was performed according to ASTM D 3359 Test Method B, using Scotch 610 tape, available from 3M Company of Saint Paul, Minn. Adhesion was generally rated on a scale of 1-10 where a rating of “10” indicates no adhesion failure, a rating of “9” indicated 90% of the coating remains adhered, a rating of “8” indicates 80% of the coating remained adhered, and so on.

Joy Detergent Test: The “Joy” test measured the resistance of a coating to a hot 82° C. Joy detergent solution. The solution was prepared by mixing 30 grams of Ultra Joy Dishwashing Liquid (product of Procter & Gamble) into 3000 grams of deionized water. Coated strips were immersed into the 82° C. Joy solution for 15 minutes. The strips were then rinsed and cooled in deionized water, dried, and immediately rated for blush as described previously.

TABLE 6 MEK Joy Double Detergent Test Bake Conditions Rubs Blush/Adhesion Example 1 1^(st) Bake: 50 10/10 15″ @ 400 F. PMT 2^(nd) Bake: 3′ @400 F. Example 1 1^(st) Bake: 50 10/10 15″ @ 320 F. PMT 2^(nd) Bake: 3′ @400 F. PPG3805803* 1^(st) Bake: 50 10/10 15″ @ 400 F. PMT 2^(nd) Bake: 3′ @400 F. PPG3805803* 1^(st) Bake: 50 10/10 15″ @ 320 F. PMT 2^(nd) Bake: 3′ @400 F. *PPG 3805803 is a commercial water reducible varnish from PPG Industries. It contains two water reducible acrylic resins and melamine (formaldehyde containing).

Example 14

The hydroxyl functional alkyl polyureas of Example 1 and Example 3 were each mixed with an internally produced acrylic latex polymer that had a solid content of 29.8% when measured after heating a sample to 110° C. for 1 hour and a measured acid value of 12.8 mg KOH/g. A suitable acrylic latex can be prepared, for example, according to the procedures outlined by Perez in U.S. Pat. No. 5,714,539. The crosslinkers of Example 1 and Example 3 were added in various amounts to achieve different ratios of COOH/OH as indicated in Table 7. To the mixtures were added 10% on solids of ethylene glycol mono-2-ethylhexyl ether (purchased from Eastman as Ektasolve EEH). The mixtures were drawn down on 0.0082″ aluminum substrate to a wet film thickness of 37 microns. The film was baked for 10 seconds in a 290° C. conveyor oven. The substrate reached a Peak Metal Temperature of 232.2° C.

After baking, the cured coatings were tested for solvent resistance using the “MEK Double Rub” test described in Example 13. The cured coating was also evaluated with the Acetic Acid Test. The Acetic Acid Test measured the resistance of the coating to a boiling 3% acetic acid solution. The solution was prepared by mixing 90 g of glacial acetic acid (product of Fisher Scientific) into 3000 g of deionized water. Coated strips were immersed into the boiling acetic acid solution for 30 minutes. The strips were then rinsed and cooled in deionized water, dried, and immediately rated for blush. Blush was measured and reported in Example 13.

As shown in the following Table 7, the solvent resistance (MEK DR) and the blush results (Acetic Acid Blush) were better when the hydroxyl alkyl functional polyuria was used.

TABLE 7 232.2° C. Peak Metal Temperature COOH/OH Ratio MEK DR Acetic Acid Blush — none 16 4 1:0.35 IPDI/HEA 68 6 1:0.55 Example 3 100 7 1:0.9  100 6 1:0.35 HDI/HEA 94 6 1:0.55 Example 1 100 6 1:0.9  100 6

In a second series of tests, the mixtures described above were drawn down on 0.0082″ aluminum substrate to a wet film thickness of 37 microns. The film was baked for 10 seconds in a 267° C. conveyor oven. The substrate reached a Peak Metal Temperature of 215.6° C.

After baking, the cured coatings were checked for solvent resistance using the MEK double rub test. As shown in the following Table, the MEK Double Rubs results improve with the inclusion of the hydroxyl alkyl functional polyuria as compared to no HAU.

TABLE 8 215.6° C. Peak Metal Temperature COOH/OH Ratio MEK DR — none 14 1:0.35 IPDI/HEA 56 1:0.55 Example 3 39 1:0.9  57 1:0.35 HDI/HEA 58 1:0.55 Example 1 54 

What is claimed is:
 1. A hydroxy functional alkyl polyurea having the formula:

wherein R comprises the residue of an isocyanurate, biuret, allophonate, glycoluril, benzoguanamine, and/or polyetheramine; wherein each R1 is independently a hydrogen, alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.
 2. The polyurea of claim 1, wherein R comprises the residue of an isocyanurate.
 3. The polyurea of claim 1, wherein at least one R1 comprises an ethanol or isopropanol group.
 4. A composition comprising: a. A film forming resin; and b. A hydroxy functional alkyl polyurea crosslinker having the formula:

wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, the residue of an isocyanurate, biuret, allophanate, glycoluril, benzoguanamine and/or polyetheramine; wherein each R1 is independently a hydrogen, an alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.
 5. The coating of claim 4, wherein R comprises a substituted or unsubstituted C2-C12 alkyl or aromatic group.
 6. The coating of claim 4, wherein R comprises a substituted or unsubstituted C6 alkyl group.
 7. The coating of claim 4, wherein R1 comprises ethanol or isopropanol.
 8. The coating of claim 4, wherein the coating is substantially formaldehyde free.
 9. The coating of claim 4, wherein the coating is a powder coating.
 10. The coating of claim 4, further comprising a catalyst.
 11. The coating of claim 10, wherein the catalyst comprises tin and/or titanium.
 12. The coating of claim 4, wherein the coating cures at a temperature of 130° C. or lower in 30 minutes or less.
 13. The coating of claim 4, wherein the coating cures at a temperature of 250° C. or lower in fifteen seconds or less.
 14. The coating of claim 4, wherein the R1 groups do not contain an ether linkage.
 15. A substrate coated at least in part with the coating of claim
 4. 16. The substrate of claim 15, wherein the substrate comprises a package.
 17. The substrate of claim 15, wherein the substrate comprises a metal can.
 18. The substrate of claim 15, wherein the substrate comprises a vehicle.
 19. The substrate of claim 15, wherein the substrate is rubber and/or plastic.
 20. A hydroxy functional alkyl polyurea having the formula

wherein R10 comprises the reaction product of an isocyanate and an alkanol amine, but the isocyanate is not HDI when the alkanol amine is diethanol amine or monomethanol amine and the isocyanate is not IPDI when the alkanol amine is monomethanol amine; wherein each R1 is independently a hydrogen, alkyl having at least 1 carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6. 